Course

Unit I

Concepts and Metal Carbonyls
History and overview on organometallic compounds. Classification and nomenclature hapticityof fragments, 18-electron and 16-electron organometallic compounds. Structure prediction based on 18 electron rule. Metal carbonyls synthesis and bonding of metal carbonyls (based on MO theory), donor and acceptor properties of CO, different types of binding modes of CO, poly-nuclear carbonyls with and without bridging groups, metal- metal bonding in M-CO clusters, cluster valence electron (CVE) count, CVE based structure prediction. IR spectral features of metal carbonyls, activation of CO by bonding with metal ions.

Unit II

Types of Organometallic Compounds
Metal phosphines compounds of transition metals, M-N2 (metal dioxygen), M-O2 (metal dioxygen), M-NO (metal nitrosyl) and M-CN (metal cyanide/isocyanide) complexes, bonding and structural features. Organometallic compounds with ?-donor ligands like olefins, acetylenes and allyl moieties. Metal derivatives of cyclic ?-donors (metallocenes, sandwich/half-sandwich compounds, bent metallocenes), metal-carbon ?- donors (metal carbenes Fischer carbenes, Schrock carbenes and N-heterocyclic carbenes, metal polyenes, metal carbines, metal alkyl/aryl derivatives). Organometallic chemistry of lithium and magnesium, aluminium alkyls and all other main-group organometallics. Structural features and nature of bonding in above compounds

Unit III

Structure and Bonding
Fragment molecular orbitals (FMO) of various organic and inorganic moieties like CH3, CH2, CH, BH2, BH, NH2, NH. FMOs (?-orbitals) of C3H5, C4H4, C4H6, C5H5, C6H6, C8H8. Inorganic fragments MLn with varying number of Ls. Symmetry and shape of their FMOs. isolobal concept, iso-electronic and isolobal relationships between various organic and inorganic (MLn) fragments. Structure and bonding between various organic and inorganic fragments based on MO level diagrams metal-olefins, MLn-cyclobutadiene, MLn-carbene, MLn- carbyne, MLn-cyclopentadienyl systems, compounds with metal-metal multiple bonds (metal-metal ?, ? and ? bonds).

Unit IV

Stereochemistry and reactions
Stereochemically non-rigid molecules, fluxional nature of organometallic compounds (including Li-C, Mg-C), characterization of non-rigidity of organometallic compounds by NMR spectroscopy. Difference in NMR spectra of fluxional organometallic compounds at high and low temperatures. Characterization techniques of organometallic compounds (by NMR 1H, 13C and 31P NMR spectroscopy, Dynamic NMR, Mass spectrometry). Reactions involving various organometallic compounds – oxidative addition reactions, reductiveelimination reactions, migratory insertion reactions, 1,1-type and 1,2-type insertion reactions, elimination reactions, ?-hydride elimination reactions. Conditions for organometallic compounds to exhibit above reactions, cyclo-metalation and ortho-metalation reactions, agnostic interactions.

Unit V

Organometallic Catalysis
Alkene hydrogenation using Wilkinson’s catalyst, water-gas shift reaction, Mosanto process, Cativa Process. Reaction steps in the above catalytic processes. Hydro-formylation reactions, catalytic addition of molecular oxygen to alkenes (Wacker process), Ziegler-Natta polymerization of alkenes, Fischer-Tropschprocess, olefin-metathesis (types of Grubbs catalysts and Hoveyda–Grubbs catalysts), oligomerization of alkynes, aluminium alkyls in polymerization of olefins. Palladium based reactions such as Heck, Stille, Suzuki, Sonogashira, Buchwald-Hartwig couplings; Tsuji-Trost C-C bond formations. Homogeneous vs. heterogeneous organometallic catalysis (principles, mechanism and their applications). Organometallics – in industry, in medicine, in agriculture and in environmental science.

• CO01: Analyze the stability, structure and reactivity of organometallic complexes with the sound knowledge of basic principles of organometallic chemistry.
• CO02: Utilize modern instrumental techniques to characterize organometallic compounds and to identify the binding mode.
• CO03: Apply the profound knowledge in various organometallic reaction types and mechanisms for efficient catalytic processes.
• CO04: Elucidate the mechanism of homogeneous organometallic catalysts and apply this knowledge for large-scale and smaller-scale production of utility chemicals.

Textbooks

1. E. Huheey, R. A. Keiter, R. L. Keiter, ‘Inorganic Chemistry – Principles of Structure and Reactivity’, 4^th Edn., Prentice Hall, 1997.
2. Atkins, T. Overton, J. Rourke, M. Weller, F. Armstrong,’ Shriver and Atkins Inorganic Chemistry’, 4^th Edn., Oxford University Press, 2006.
3. A. Cotton, G. Wilkinson, C. A. Murillo, M. Bochmann, ‘Advanced Inorganic Chemistry’, 6^th Edn., Wiley- Interscience, 1999.
4. Anil Elias,Gupta B.D.,“Basic Organometallic Chemistry”,Universities Press; 2^nd Edition 2013
5. D. Atwood, ‘Inorganicand Organometallic Reaction Mechanism’, 2^ndEdn.,Wiley

References

1. R. H. Crabtree, ‘Organometallic Chemistry of the Transition Metals’, John Wiley & Sons, 6^thEd.2. VCH,1997.
2. Tsuji,‘Transition metal reagents and catalyst innovations in organic synthesis’,John-Wiley-& Sons, Ltd, New York, 2000
3. E. Douglas, D. H. McDaniel, J. J. Alexander, Concepts and Models of Inorganic Chemistry, 3^rd Edn., Wiley – India, 2007.
4. Bochmann, Orgaonometallics: Complexes with Transition Metal-Carbon Sigma Bonds, Oxford University Press, 1994.
5. J .P. Collman, R G Finke and J R Norton “Principles and Applications of Organo-transition metal Chemistry” University Science Books,1987.
6. K. Li, G. D. Zhou, T. Mak, Advanced Structural Inorganic Chemistry, Oxford University Press,2008.
7. C. Nicolaou,‘Classics in Total Synthesis’, VolsI-III, Wiley-VCH, 1996; 2003; 2011